Compositions of polyepoxides, ammonia derivative-aldehyde condensates and mixed esters



United Sm Sylvan 0. Greenlee, Racine, Wis, assignor to S. C. Johnson &Son, Inc., Racine, Wis.

No Drawing. Application November 19, 1956 Serial No. 622,753

12 Claims. (Cl. 260-21) This invention relates to new products andcompositions resulting from the reaction of ammonia derivative-aldehydecondensates, polyepoxides and mixed esters prepared fromhydroxyaryl-substituted aliphatic acids, modifying organic acids, andpolyhydric alcohols, the compositions being valuable in the manufactureof varnishes, molding compositions, adhesives, films, molded articles,etc. According to the present invention, the ammonia derivative-aldehydecondensate, polyepoxide materials and mixed esters may be reacted inregulated proportions to produce initial reaction mixtures as well asintermediate and final reaction products.

An object of this invention is the production of compositions containingammonia derivative-aldehyde condensates, polyepoxides and mixed estersof hydroxyarylsubstituted aliphatic acids, modifying organic acids, andpolyhydric alcohols in proportions suitable for reaction to form resins,films, coating compositions, etc.

Another object of this invention is the production of intermediatereaction products from initial reaction mixtures of these ammoniaderivative-aldehyde condensates, polyepoxides and mixed esters capableof further reaction on the application of heat to form insoluble,infusible products.

Another object of this invention is the production of initial andintermediate reaction mixtures of the hereinbefore described characterwhich are stable at ordinary temperatures for relatively long periods oftime yet which may be converted to polymeric products upontheapplication of heat.

Still another object of this invention is the production of finalreaction products from these initial and interme-. diate reactionmixtures characterized by such physical properties as hardness,flexibility, and toughness, and such chemical properties as resistanceto the chemicals and Water. These and other objects and advantages areattained by the present invention, various novel features of which willbecome more fully apparent from the following description withparticular reference to specific examples which are to be considered asillustrative only.

In the preparation of polymeric, infusible, and Il'lSOlllr blecompositions for use in protective coating films, molding compositions,adhesives, etc., one of the major problems is to obtain a product whichpossesses the necessary hardness but which still retains the desiredflexibility and toughness. In the plastics field, polyepoxides have beenwidely used in preparing such polymers although a recognized majorproblem has continued to be a method of plasticizing the compositions.

In this invention it has been found that the poly cpoxides reacted withthe herein described mixed esters and aldehyde condensates provide a newseries of compositions possessing a number of outstanding properties. Bythe proper selection of the mixed ester and aldehyde condensate suchproperties as flexibility, hardness, gloss, water and chemicalresistance, and air-drying or heat-converting characteristics can beeasily imparted and readily regulated. These characteristics areincorporated into .fitice the composition by primary chemical bondingand, therefore, no problem exists of plasticizer migration or lossthrough volatilization.

In general, the cpoxides contemplated for use are compounds containingan average of more than 1 up to about 20 epoxide groups per molecule.Such compounds, free from functional groups other than epoxide andhyroxyl, are reacted with active hydrogen-containing groups, such as thehydroxyl groups supplied by the mixed esters herein contemplated.Typical epoxides which have been found to be operable are resinouspolyepoxides, resinous polyepoxide-polyesters, epoxidized natural oils,and simle aliphatic polyepoxides.

The mixed esters contemplated for use are those prepared from polyhydricalcohols, modifying organic acids, and hydroxyaryl-substituted aliphaticacids. Variations can be obtained in the mixed ester through judiciousselection of the modifying organic acid and polyhydric alcohol. Theammonia derivative-aldehyde condensates are the reaction products of anammonia derivative with aldehydes, the variation in properties areobtained from the proper selection of the ammonia derivative and thealdehyde.

The mixed esters generally are conveniently prepared by esterifyingpolyhydric alcohols with a mixture of an bydroxyaryl-substitutedaliphatic acid and a modifying organic acid under conditions whereby thearyl hydroxyl groups of the hydroxyaryl-substituted aliphatic acid aresubstantially unreacted. Since these aryl-hydroxyl groups are moreacidic in nature than the alcoholic hydroxyl groups of the polyhydricalcohols, the reaction of arylhydroxyl groups will be insignificant inthose cases where thereaction mixtures contain about equivalent amountsor more of alcoholic hydroxyl groups for each equivalent of carboxylgroups, and generally it was found that excellent products were obtainedusing such proportions.

The hydroxyaryl-substituted aliphatic acid contemplated for use hereinshould have two hydroxyaryl groups attached to a single carbon atom. Thepreparation of such an aryloxy acid is most conveniently carried out bycondensing a keto-acid with the desired phenol. Experience in thepreparation of bisphenol and related compounds indicates that thecarbonyl group of the keto-acid should be positioned next to a terminalmethyl group in order to obtain satisfactory yields. Prior applications,Serial Nos. 464,607 and 489,300, filed October 25, 1954, and February18, 1955, respectively, disclose a number of illustrative compoundssuitable for use as the Diphenolic Acid and methods of preparing thesame. These materials, which are referred to for convenience asDiphenolic Acid or DPA, consist of the condensation products oflevulinic acid and phenol, substituted phenols, or mixtures thereof. Itis to be understood that the phenolic nuclei of the Diphenolic Acid maybe substituted with any groups which will not interfere with thereactions contemplated herein. For example, the nuclei may be alkylatedwith alkyl groups of from 1-5 carbon atoms as disclosed in my copendingapplication Serial No. 489,300 or they may be halogenated. TheDiphenolic Acid derived from substituted phenols, such as the alkylatedphenols, are sometimes more desirable than the products obtained fromunsubstituted phenols since the alkyl groups provide better organicsolvent solubility, flexibility, and water resistance. However, theunsubstituted product is usually more readily purified.

Polyhydric alcoholswhich may be used in the prepara tion of the mixedesters include both the resinousand nonresinous-type alcohols.Illustrative of the nonresinous-type of polyhydric alcohols are suchmaterials as ethylene glycol, polyethylene glycols, propylene glycol,polypropylene glycols, 1,4-butanedio1, 2,5-pentanediol, 1,6-hexanediol,neopentyl glycol, glycerol, erythritol,

3 pentaeryt-hritol, polypentaerythritols, sorbitol, mannitol,alpha-methyl glucoside, polyallyl alcohols, diethanolamine,triethanolamine and tetramethylol cyclohexanol.

The resinous polyhydric alcohols which may be employed can beillustrated by such products as those prepared by the reaction ofphenol-formaldehyde condensates with chlorohydrins. For example, analkyl phenol may be condensed with formaldehyde to form an intermediatemethanol derivative and an alkaline solution of this intermediate maythen be treated with a chlorohydrin, such as glycerol monochlorohydrin,to yield after condensation a polymeric polyhydric alcohol. Still otherresinous polyhydric alcohols may be illustrated by the alcoholic epoxideresins which are polyether derivatives of polyhydric phenols and suchpolyfunctional materials as polyhalohydrins, polyepoxides, orepihalohydrins. Reaction products may be prepared'which are monomeric orpolymeric polyhydric alcohols having aliphatic chains and aromaticnuclei connected to each other by ether linkages and containing terminalepoxide groups. Preparations of these epoxide materials, as well as someillustrative examples, are described in US. Patents 2,456,408,2,615,007, 2,615,008, 2,503,726, 2,668,805, 2,668,807, and 2,698,315.Well-known commercial examples of these resins are the Epon resinsmarketed by the Shell Chemical Corporation.

The modifying organic acids employed with the hydroxyaryl substitutedaliphatic acids in preparing the mixed esters used in this inventioninclude a wide variety of aliphatic or aromatic resinous or nonresinous,shortor long-chain, saturated or unsaturated materials. The selection ofthe modifying acid depends upon the characteristics which are desired inthe final polymeric products of this invention.

Self-plasticized compositions, which in addition have air-dryingcharacteristics, may be prepared by employing as the modifying organicacid the drying oil fatty acids.

These acids normally contain from about 18 to 22 carbonv atoms and areobtained by the saponification of naturally occurring unsaturatedvegetable oils. Other acids may be illustrated by the fish oil acids andthe shorter chain unsaturated acid, undecanoic acid which is. adecompositionproduct of castor oil acids. Mixedesters prepared;

from the materials suitable for, use in this invention are more fullydescribed in a copending application of Greenlee, filed April 11, 1955,having Serial No. 500,696 entitled Mixed Esters. Low molecular Weightunsaturated acids may also be used if only airdrying or heat-convertingcharacteristics are desired since the plasticization effect of the lowmolecular. weight materials is insignificant. sorbic acid.

The saturated monobasic aliphatic acids may also be used in theproduction of the mixed esters. Such acids.

Examples of such acids are crotonic acid and matic acids also arevaluable as the modifying organic acid and may be illustrated by suchmaterials as benzoic acid, butyl benzoic acid, phthalic acid, naphthoicacid, and phenoxy acetic acids. These acids are useful in impartinghardness, rigidity, and toughness to the polymeric products derivedtherefrom. The modifying acids used in the preparation of the mixedesters also include the dibasic acids such as succinic acid, azelaicacid, sebacic acid, and longer chain acidsv such as the 36 carbon acidsprepared by dimerizing unsaturated vegetable oil acids. 'In thepreparation of the mixed esters from polyhydric alcohols,hydroxyaryl-substituted acids and modifying organic acids, the reactantsmay be used in varying proportions of wide ranges.

The ratio of acid topolyhydric alcohol may be adjusted so thatsubstantially equivalent amounts of carboxyl and hydroxyl groups arepresent in the mixture. Such compositions have been found to beparticularly valuable. However, it is recognized that the hydroxylcontent of the mixture can be increased greatly so as to besubstantially in excess of carboxyl groups, for example, in the range ofabout 5 :1, although such products are of value, it is consideredundesirable to increase this ratio since the effect of the DPA andmodifying acid is thereby virtually lost.

Similarly, the ratio of hydroxyaryl-substituted acid to the modifyingorganic acid may be proportioned within.relatively large ranges.Remarkable products were ob tained,.for example, when the ratio ofhydroxyaryl-substitutedacid to modifying organic acid ranged from about1:5 and 5:1. The particular ratio employed, of course, would depend uponthe choice of modifying acid and the modifications desired in thereaction mixtures and polymeric materials prepared from the mixedesters.

The mixed esters of this invention are conveniently prepared by directheating at temperatures of from 190275 C. with provision forthecontinuous removal of water produced by the condensation. phenolic Acidand-many of the modifying organic acids,

I as well as the polyhydric alcohols, have relatively high and fish oilacids, the unsaturated acids being first hydrogenated to remove theirunsaturation. Longer chain.

saturated acids maybe obtained by the saponification of naturallyoccurring waxes or by chemical synthesis using the so-called Oxoprocess.

Mixed esters prepared from resinous acids are advantageously employed insome instances. For example, rosin acids are generally used in thepreparation of polymeric products to impart hardness, gloss, and otherresinous characteristics. Mixed esters prepared from such materialsasthese rosinacids may be advantageously The preparation of such mixedesters is more. fully described inv the copending application ofGreenlee' entitled Mixed Resin Acid Esters, Serial No. 519,279, filedJune 30, 1955. Aro-.

employed in this invention.

boiling points, which are in most cases above C., water may be removedby permitting it to volatilize during esterification. In the case of thepreparation of the esters of more volatile organic acids, it-isconvenient to use the anhydrides or sometimes the acid chlorides. For

example, the preparation of a mixed ester containing the acetate wouldconveniently be prepared by using acetic anhyd'rideforthe-esterification. Inthepreparation of the higher esters where hightemperature is used, removal of the water may be facilitated bycontinuously bubbling through the reaction mixture during esterificationa stream of inert gas, such as carbon dioxide or nitrogen. It'is alsosometimes convenient to facilitate the Water removalby carrying out thereaction in a vessel provided with a condenser attached thereto througha water trap. A sufficient amount of a volatile water insoluble solventis added in order to obtain reflux at the esterification temperature.The water is continually removed by azeotropic distillation, permittingthe solvent to return to the reaction mixture after having dropped theWater in the.

water trap.

The order of addition of the various ingredients, Diphenolic, Acid,modifying organic acid, and polyhydric.

alcohol, to each other may be varied. It is sometimes advantageous to.vary the order of reaction to obtain optimum results with a particularcombination of ingrcdi ents used. In the art of high temperatureesterification;

It will be'obvious to those skilled inthe art that a Since theDiparticular combination of physical properties may be obtained for thepolymeric products of this invention by employing a mixture ofpolyhydric alcohols and/or a mixture of modifying acids. Thus productswhich include various combinations of such reactants are also consideredto be within the scope of the present invention.

Examples I through IX, inclusive, describe the preparation of mixedesters of Diphenolic Acid, modifying organic acids and polyhydricalcohols. The reactions were, in general, carried out in a 3-neckedflask provided with a mechanical agitator, thermometer, and a water trapattachment for the condenser. The removal of water formed duringesterification was facilitated by the utilization of azeotropicdistillation with a small amount of xylene, the xylene being sufficientto give refluxing at the temperature of esterification. The proportionsgiven are expressed as parts by weight unless otherwise indicated. Acidvalue represents the number of milligrams of KOH required to neutralizea l-gram sample. The acid values were determined by direct titration.Softening points were determined by Durrans Mercury Method (Journal ofOil and Color Chemists Association, 12, l73-175 19291).

EXAMPLE 1 A mixture of 143 parts of 4,4-bis(4-hydroxyphenyl)- pentanoicacid and 70 parts of soyabean oil fatty acids was heated to 230 C; atwhich point 38 parts of dipentaerythritol were added over a period of 10minutes. The reaction mixture was held at 230240 C. for a period of 5hours, during the last minutes of which time the pressure was reduced toabout millimeters. The resulting product, amounting to 227 parts, had anacid value of 2.8 and a softening point of 80 C.

EXAMPLE 2 A mixture of 51 parts of glycerol,140 parts of dehydratedcastor oil acids and 286 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acidwas heated over a period of 30 minutes to 90 C. and to 240 C. over aperiod of another hour. The reaction mixture was held at 240-245 C. fora period of 4 /2 hours. The resulting product amounting to 448 parts hadan acid value of 9.5 and a softening point of 65 C.

EXAMPLE 3 A mixture of 278 parts of Epon resin 1004 and 224 parts oflinseed oil acids was heated at 220224 C. for a period of 1 /2 hours. Tothis mixture was added 57.2 parts of 4,4-bis(4-hydroxyphenyl)pentanoicacid and the heating continued at 230-240 C. for an additional 2 /2hours. The resulting product had an acid value of 7 and a softeningpoint of 63 C.

EXAMPLE 4 A mixture of 280 parts of dehydrated castor oil acids and 149parts of pentaerythritol was heated to 235 and held at this temperaturefor a period of 1 /2 hours, at which point 797 parts of4,4bis(4-hydroxyphenyl)- pentanoic acid was added and the heatingcontinued at 210 C. for 6 /2 hours. The reaction mixture was finallyheated to 240 C. over a period of /2 hour during which time the pressurewas reduced to 20 millimeters. The resulting product amounted to 1130parts and had an acid value of 7.6 and a softening point of 69 C.

EXAMPLE 5 A mixture of 172 parts of 4,4-bis(4-hydroxyphenyl) pentanoicacid and 56 parts of linseed oil acids was heated to 220 C. at whichpoint 30 parts of pentaerythritol were added slowly over a period of 12minutes and the reaction continued at 215-225 C. for a period of 6hours. The pressure was reduced to around 20 millimeters during thelatter 18 minutes of the reaction period. The product, amounting to 232parts, had an acid value of 5 and a softening point of 79 C.

EXAMPLE 6 A mixture of 280 parts of China-Wood oil acids and 150 partsof pentaerythritol was heated at 225 C. until the acid value had reached6. To this mixture was added 850 parts of4,4-bis(4-hydroxyphenyl)pentanoic acid and the reaction mixture heatedfor a period of 2 hours at 210-220 C. The pressure was reduced to 30millimeters during the last 20 minutes of heating. The resulting producthad a softening point of C.

EXAMPLE 7 A mixture of 343 parts of 4,4-bis(4-hydroxyphenyl)- pentanoicacid, 227 parts of steanic acid and 68 parts of glycerol was heated fora period of 1 hour at 203-220 C. and for a period of 4 hours at 220248lC. to give a product having an acid value of 2.9.

EXAMPLE 8 A mixture of 286 parts of 4,4-bis(4-hydroxyphenyl)- pentanoicacid, 280 parts of soyabean oil acids and 68 parts of ethylene glycolwas heated for a period of 40 minutes at 225 C. and for an additionalperiod of 5 hours at 225-238 C. to give a product having an acid valueof 9.5.

EXAMPLE 9 A mixture of 286 parts of 4,4-bis(4-hydroxyphenyl)- pentanoicacid, 280 parts of China-wood oil acids and 68 parts of ethylene glycolwas heated for a period of 6 hours at 220-237 C. to give a producthaving an acid value of 2.9.

Illustrative of the epoxide compositions which may be employed in thisinvention are the complex. epoxide resins which are polyetherderivatives of polyhydric phenols with such polyfunctionalcouplingvagents as polyhalohydrins, polyepoxides, or epihalohydrins.These compositions may be described as polymeric polyhydric alcoholshaving alternating aliphatic chains and nuclei connected to each otherby ether linkages, containing terminal epoxide groups and free fromfunctional groups other than epoxide and hydroxyl groups. It should beunderstood that significant amounts of the monomeric reaction productsare often present. This would be illustrated by I to III below where nequals zero. Preparation of these epoxide materials as well asillustrative examples are described in US. Patents 2,456,408, 2,503,726,2,615,007, 2,615,008, 2,668,807, 2,688,805, and 2,698,315. Well-knowncommercial examples of these resins are the Epon resins marketed by theShell Chemical Corporation. Illustrative of the preparation of theseepoxide resins are the following reactions wherein the difunctionalcoupling agent is used in varying molar excessive amounts:

Polyhydric phenol and an epihalohydrinbis(hydroxyphenyl)isopropylidene-l-excess epiehlorohydrin Y CHPolyhydrte phenol and a polyepoxlde bls(hydroxyphenyl)isopropylideneexcess butylene dioxide O H1 CHCHHOHr-O OCHBOHOHCHOHGHE I OCHzCHOHCHOH:heat Q a n Ofi CH; II

Polyhydric phenol and a polyhalohydrinbisthydroxyphenyl)isopropylidene+excess alpha-glycerol diehlorohydrtn 0C H2GHCHT O OOHrOHOHOHz- O OCHzGHCHr aqueous alkali CH3 CH3 n CH3 CH3 InAs used in the above formulas, It indicates the degree of polymerizationdepending on the molar ratio of re actants; As can be seen from theseformulas, the complex epoxide resins used in this invention containterminal epoxide groups and alcoholic hydroxyl groups attached to thealiphatic portions of the resin, the latter being formed by thesplitting of epoxide groups in the reaction of the same with phenolichydroxyl groups. reaction with the phenolic hydroxyl groups of thepolyhydric phenols is generally accomplished by means of epoxide groupsformed from halohydrins by the loss of hydrogen and halogen as shown bythe following equation:

Other epoxide compositions Which may be used include the polyepoxidepolyesters which may be prepared by esterifying tetrahydrophthalicanhydride with a glycol and epoxidizing the product of theesterification reaction. In the preparation of the polyesters,tetrahydrophthalic acid may also be used as well as the simple esters oftetrahydrophthalic acid such as dimethyl and die-thyl esters. There is atendency with tertiary glycols for dehydration to occur under theconditions used for esterification so that generally the primary andsecondary glycols are the most satisfactory in the polyester formation.Glycols which may be used in the preparation of this polyestercomposition comprise, in general, those glycols having two hydroxylgroups attached to separate carbon atoms and free from functional groupswhich would interfere with the esterification or epoxidation reactions.These glycols include such glycols as ethylene glycol, diethyleneglycol, triethylene glycol, tetramethylene glycol, propylene glycol,polyethylene glycol, neopentyl glycol, and hexa. methylene glycol.Polyepoxide polyesters may be pre- .pared from these polyesters byepox-idizing the unsaturated portions of the tetrahydrophthalic acidresidues in the polyester composition. By properly proportioningreactants in the polyester formation and regulating the epoxidationreaction, polyepoxides having up to 12 or more epoxide groups permolecule may be readily pre pared. These polyepoxide polyestercompositions, as well as their preparation, are more fully described inUltimately, the

a copending applicationhaving Serial No. 503,323, filed April 22, 1955.

Polyepoxidecompositions useful in this invention also include theepoxidized unsaturated natural oil acid esters,

including the unsaturated vegetable, animal, and fish oil acid estersmade by reacting these materials with various:

by simple monohydric alcohols such as methyl, ethyl,

or decyl alcohol, by polyhydric alcohols such as glycerol,

pentaerythritol, polyallyl alcohol, or resinous polyhydric Also suitableare the mixed esters of polyalcohols. carboxylic acids and long chainunsaturated natural oil acids with polyhydric alcohols, such as glyceroland pentaerythritol. tain from more than 1 up to 2 0 epoxide groups permolecule. The method of epoxidizing these unsaturated oil acid estersconsists of treating them with various oxidizing agents, such as theorganic peroxides and the peroxy acids, or with one of the various formsof hydrogen peroxide. A typical procedure practiced in the art consistsof using hydrogen peroxide in the presence of an organic acid, such asacetic acid and a catalytic material, such as sulfuric acid. Morerecently epoxidation methods have consisted of replacing the mineralacid catalyst with a sulfonated cation exchange material, such as thesulfonated copolymer of styrene divinylbenzene.

The epoxide compositions which may be used in preparing the compositionsof this invention also include the simple aliphatic polyepoxides whichmay be illus trated by the products obtained by polymerizing allylglycidyl ether through its unsaturated portion as illustrated by thefollowing:

0 CH2=CHCH OHCH OHzOCHzOHOHg peroxide I CHzCHCHi OHCHzCHqOOHgCHCH;

This reaction may be carried further to give higher polymers than thedimer shown. Other aliphatic polyepoxides useful in this invention maybe illustrated by the poly(epoxyalkyl) ethers derived from polyhydric alcohols. These materials may, in general, be prepared by reacting analiphatic polyhydric alcohol with an epi halohydrin in the presence of asuitable catalyst and in turn dehydrohalogenating the product to producethe epoxide composition. The production of these epoxides may beillustrated by the reaction of glycerol with epichlorohydrin in thepresence of boron trifluoride followed These epoxidized oil acid estersmay conby dehydrohalogenation with sodium aluminate as follows:

onion BFa OHOH soruononloi on on CHzOCHzCHOHCHzCl onzooruonom o mono,onoontonononzoi CHOCHzCHCHZ ornoornonorromor omoomonon,

It is to be understood that such reactions do not give pure compoundsand that the halohydrins formed and the epoxide derived therefrom are ofsomewhat varied character depending upon the particular reactants, theirproportions, reaction time and temperature. In addition to epoxidegroups, the epoxide compositions may be characterized by the presence ofhydroxyl groups and halogens. Dehydrohalogenation affects only thosehydroxyl groups and halogens which are attached to adjacent carbonatoms. Some halogens may not be removed in this step in the event thatthe proximate carbinol group has been destroyed by reaction with anepoxide group. These halogens are relatively unreactive and are not tobe considered as functional groups in the conversion of the reactionmixtures of this invention. The preparation of a large number of thesemixed polyepoxides is described in the Zech patents, U.S. 2,538,072,2,581,464, and 2,712,000. Still other polyepoxides which have been foundto be valuable are such epoxide compositions as diepoxy butane, diglycidether, and epoxidized polybutadiene.

Immediately following is a description or illustration of preparationsof polyepoxides which will be used to prepare the polymeric compositionsof this invention.

The complex resinous polyepoxides used in the examples and illustrativeof the commercially prepared products of this type are the Epon resinsmarketed by Shell Chemical Corporation. The following table gives theproperties of some Epon resins which are prepared by the condensation inthe presence of alkali of bis(4-hydroxyphenyl)isopropylidene with amolar excess of epichlorohydrin in varying amounts.

Melting Viscosity 1 Epoxide Average Epon resin type point, C.(Gardnerequivalent molecular Holdt) weight Based on 40% nonvolatile inbutyl Carbitol at 25 0.

Examples through 12 describe the preparation of typical polyepoxidepolyesters.

EXAMPLE 10 Preparation of polyester from tetrahydrophthalic anhydrideand ethylene glycol Epoxida tion of the polyester resin In a 3-neckedflask provided with a thermometer, a

mechanical agitator, and a reflux condenser was placed 107 parts of thedehydrated acid form of a cation exchange resin (Dowex 50-X-8, 50-100mesh, Dow Chemical Company, a sulfonated styrene-divinylbenzenecopolymer containing about 8% divinylbenzene, the percent divinylbenzeneserving to control the amount of crosslinkage. The Dowex resins arediscussed in publications entitled Ion Exchange Resins No. 1? and IonExchange Resins No. 2, copyright 1954 by Dow Chemical Company, thepublications having form number Sp32-254 and Sp31-354, respectively) and30 parts glacial acetic acid. The mixture of cation exchange resin andacetic acid was allowed to stand until the resin had completely taken upthe acid. To this mixture was added 200 parts of the polyester resindissolved in an equal weight of xylene. To the continuously agitatedreaction mixture was added dropwise over a period of 45 minutes to 1hour, 75 parts of 50% hydrogen peroxide. The reaction temperature washeld at 60 C. requiring the application of some external heat. (In somepreparations involving other polyester resins, suflicient exothermicheat is produced during the addition of hydrogen peroxide so that noexternal heat is required, or even some external cooling may berequired.) The reaction was continued at 60 C. until a milliliter sampleof the reaction mixture analyzed. less than 1 milliliter of 0.1 N sodiumthiosulfate in an iodometric determination of hydrogen peroxide. Theproduct was then filtered, finally pressing the cation exchange resinfilter cake. The acid value of the total resin solution was 42. Thepercent nonvolatile of this solution amounting to 400 parts was 50. This400 parts of solution was thoroughly mixed with 110 parts of thedehydrated basic form of Dowex 1 (an anion exchange resin of thequaternary ammonium type. Dowex 1 is a styrene-divinylbenzene copolymerillustrated by the formula RR N Ol-l where R represents thestyrene-divinylbenzene matrix and R is a methyl group, manufactured bythe Dow Chemical Company). The resulting mixture was then filteredfollowed by pressing as much as the solution as possible from the anionexchange resin cake. This product had an acid value of 4.5 and anepoxide equivalent of 288 based on a nonvolatile resin content of 42.0%.The epoxide values as discussed herein were determined by refluxing for30 minutes a Z-gram sample with 50 milliliters of pyridine hydrochloridein excess pyridine. (The pyridine hydrochloride solution was: preparedby adding 20 milliliters of concentrated HCl to a liter of pyridine.)After cooling to room temperature, the sample is then back-titrated withstandard alcoholic sodium hydroxide.

EXAMPLE 1 1 Following the procedure of Example 10, a polyester EXAMPLE12 The process of Example 10 was followed to obtain a polyester resinfrom 1.1 mols of tetrahydrophthalic anhydride, 1 mol of 1,4-butanedioland 0.2 mol of n-butanol. The product had an acid value of 8.6. Thispolyester resin was epoxidized in the same manner to give an epoxideequivalent weight of 292 and an acid. value of 5-2 11 on the nonvolatilecontent. The nonvolatile content of this resin solution was 41.9%.

Examples 13 and 14 describe the preparation of epoxidized vegetable oilacid esters.

EXAMPLE 13 Epoxidized soyabean oil acid modified alkyd resin (a)Preparation of alkyd resin.-To a kettle provided with a condenser wasadded 290 parts of white refined soyabean oil. While bubbling acontinuous stream of nitrogen through this oil, the temperature wasraised -to 250 C., at which temperature 0.23 part of litharge was addedand the temperature held at 250 C. for minutes. While holding thetemperature above 218 C., 68 parts of technical pentaerythritol wasadded after which the temperature was raised to 238 C. and held until amixture of 1 part of the product and 2 /2 parts of methyl alcohol showedno insolub'ility (about 15 minutes). At this point 136 parts of phthalicanhydride were added and the temperature gradually raised to 250 C. andheld at this temperature for 30 minutes. At this point the condenser wasremoved from the kettle and the pressure reduced somewhat by attachingto a water aspirator evacuating system. With continuous agitation themixture was held at 250 C. until the acid value had reached 10.5. Atthis point the resin was thinned with xylene to 48% nonvolatile contenthaving a viscosity of H (Gardner Bubble Viscosimeter).

(b) Epoxidation of a soyabean oil acid modified alkyd resin-In a3-necked flask provided with a thermometer,

a mechanical agitator and a reflux condenser was placed 70 parts ofdehydrated acid form of a cation exchange resin (Dowex 50-X-8) and 15parts glacial acetic acid. The mixture of cation exchange resin andacetic acid Was allowed to stand until the resin had completely taken upthe acid. To this mixture was added 315 parts of the alkyd resinsolution described in the above paragraph and 190 parts of xylene. Tothe continuously agitated reaction mixture was added dropwise 38 partsof 50% hydrogen peroxide. The reaction temperature was held at 60 C.until a milliliter sample of the reaction mixture analyzed less than onemilliliter of 0.1 N sodium .thiosulfate in an iodometric determinationof hydrogen peroxide. The product was then filtered, finally pressingthe cation exchange resin filter cake. The epoxide equivalent on thenonvolatile content was 475.

In order to remove the free acidity from the epoxidized product, 400parts of the solution were thoroughly mixed with 110 parts of thedehydrated basic form of Dowex 1 (an amine type anion exchange resin).The resulting mixture was then filtered, followed by pressing as much ofthe solution as possible from the anion exchange resin cake.

EXAMPLE 14 Epoxidized soyabean oil Admex 710, an epo-xidized soyabeanoil having an equivalent weight to an epoxide of 263,. was dissolvedin'methyl ethyl ketone to a non-volatile content of,50%. Admex 710, aproduct of the Archer-Daniels-Midland Company, has an acid value of 1, aviscosity of 3.3 stokes at 25 C. and an average molecular weight of 937.

Examples 15 and 16 describe the preparation of simple aliphaticpolyepoxides.

EXAMPLE 15 a reflux condenser was added 900 parts of dioxane and 300parts of powdered sodium aluminate.

heated to 92 C. over a period of 1 hour and 5-0 minutes, andheld at thistemperature for 8 hours and 50 minutes. After cooling to roomtemperature, the inorganic material was removed by filtration. Thedioxane and low boiling products were removed by heating the filtrate to205 C. at 20 mm. pressure to give a pale yellow product. The epoxideequivalent of this product was determined by treating a l-gram samplewith an excess of pyridine containing pyridine hydrochloride (made byadding 20 cc. of concentrated hydrochloric acid per liter of pyridine)at the boiling point for 20 minutes and back-titrating the excesspyridine hydrochloride with 0.1 N sodium hydroxide using phenolphthaleinas indicator and considering one HCl as equivalent to one epoxide group.The

epoxide equivalent on this product was found to be 152.

EXAMPLE 16 In a 3-neoked flask provided with a thermometer, a

mechanical agitator, a reflux condenser and a dropping funnel was placed402 parts of allyl glycidyl ether. With continuous agitation thetemperature was raised to C. at which time one part of a solution ofmethyl ethyl ketone peroxide dissolved in diethyl phthalate to a 60% Thealdehyde-ammonia deiivative condensation products contemplated for usein preparing the compositions herein described are formed by thecondensation products of aldehydes, particularly formaldehyde, withamines or amides, or mixtures thereof. The reactions which produce suchcondensation products involve the removal of amino or amido hydrogenatoms from the ammonia derivative. Therefore, it should be understoodthat an ammonia derivative, in order to be suitable for condensationwith an aldehyde, must contain at least one hydrogen atom attached tothe nitrogen atom. Fusible materials of varying degrees of condensationmay be used with the epoxides and the mixed esters to form the newcompositions and reaction products of this invention. Thus, thecondensates may be made by various processes known in the art for themanufacture of aldehyde-am monia derivative resins, resulting inwater-soluble, alcohol-soluble or oil-soluble types.

For use herein, the aldehyde-ammonia derivative condensate may be in itsmonomeric form which is essentially an alkylol or polyalkylol product orit may be highly condensed. It is suitable as long as it still fusibleand is soluble in or compatible with the epoxide composition and themixed esters with which it is to be reacted.

Many of the commercial products derived from the reaction of urea,thiourea, or melamine with formaldehyde are mixed products made byreacting the formaldehyde with mixtures of these materials. Suchcomposite or mixed reaction products can advantageously be used forreaction with the epoxides and the mixed esters according to the presentinvention. In addition, many of the present day commercial resinsderived from aldehydes and urea, thiourea, or melamine or a mixturethereof, are

prepared in. the presence of alcoholic or other solvents. which takepart in the reaction and become an integral with continuous agitationthis reaction mixture was gradually.

The distillation was started at 19 part of the resulting resincomposition. This is illustrated by the products prepared in thepresence of butyl alcohol in which case the butyl alco'tol to someextent condenses with the alkylol groups of the aldehyde condensate togive butyl ether residues as a part of the final composition. Suchmodified products are also suitable. In some cases it may be desirableto use an ammonia derivative aldehyde condensate which is completelysoluble in a common solvent or a mixture of solvents used to dissolvethe epoxide and the mixed esters. Solutions prepared in this manner canbe applied as a coating and the solvent subsequently evaporated beforethe main reaction between the epoxide, mixed ester, and aldehydecondensate takes place.

Examples 17 through 21, inclusive, describe the preparation ofammonia-derivative condensates used in this invention.

EXAMPLE 17 In a 3-liter 3-necked flask provided with a mechanicalagitator, a thermometer, and reflux condenser was placed 120 parts ofurea, 600 parts of 37% aqueous formaldehyde, and 1040 parts of n-butylalcohol. With continuous agitation the reaction mixture was heated toreflux temperature and the refluxing continued for a period of 1 hour.At this point a water trap Was placed between the reflux condenser andflask and filled with toluene. Distillation was continued until 315parts of water were removed from the reaction mixture. The resultingmixture was cooled to room temperature, filtered, and 1030 parts of aclear, water-white, syrupy liquid isolated.

EXAMPLE 18 The procedure of preparation, including the water removal,was the same as that used in Example 17. A mixture of 304 parts ofthiourea, 960 parts of 37% aqueous formaldehyde, and 800 parts ofn-butyl alcohol was used to give a final yield of 1214 parts of a clear,light amber, syrupy product.

EXAMPLE 19 The procedure of preparation, including the removal of water,was the same as that used in Example 17. A mixture of 120 parts of urea,148 parts of thiourea, 950 parts of 37% aqueous formaldehyde, and 800parts of n-butyl alcohol was used to give a final yield of 1175 parts ofa clear, almost colorless, syrupy liquid.

EXAMPLE 20 In a 3-liter 3-necked flask provided with a mechanicalagitator, a thermometer, and a reflux condenser was placed 378 parts ofmelamine, 840 parts of 37% aqueous formaldehyde, and 725 parts ofn-butyl alcohol. With continuous agitation the reaction mixture washeated to reflux temperature and the refluxing continued for a period of30 minutes. At this point a water trap was placed in the distillingcolumn between the flask and the agitator, a thermometer, and a refluxcondenser was placed 370 parts of p-toluenesulfonamide and 640 parts of37 aqueous formaldehyde the pH of which had been previously adjusted to6.0 with potassium acid phthalate and sodium hydroxide. With continuousagitation the reaction mixture .was heated to reflux temperature over aperiod of 40 minutes and the refluxing continued for a period of 15minutes. At this point the reaction mixture was allowed to cool and thewater decanted from the resin. The resin was washed 3 times with warmwater and finally dehydrated in vacuum at 30-50 pressure, using amaximum flask temperature of C. to yield 1245 parts of water-whiteresinous solid.

In general, in making the new compositions, the poly epoxides, the mixedesters, and the ammonia derivativealdehyde condensates are compounded insuitable propor tions, either with or without the addition of acatalyst, the reaction will then proceed to completion with theapplication of heat. More specifically, the reaction is effected byheating the mixed materials at elevated temperatures usually in therange of -250 C. The addition of a catalyst is usually unnecessary;however, in certain cases it may be desirable to use small amounts ofcatalysts, such as the boron trifluoride adducts, sodium phenoxides, ortraces of certain amine-type compositions.

The reaction mixtures and final reaction products of this invention maybe prepared by using varying proportions of mixed ester, epoxide, andaldehyde condensate. For instance, if relatively flexible finalconversion products are desired, they may be advantageously prepared byusing an excess of a relatively soft linear epoxide resin with lesseramounts of a relatively hard aldehyde condensate or by employing anexcess of a relatively soft aldehyde condensate with lesser amounts ofthe harder complex epoxide resins. Conversely, a harder conversionproduct could be prepared by using an excess of a relatively hardcomplex epoxide resin with lesser amounts of the softer predominantlylinear aldehyde condensate or by using an excess of a relatively hardaldehyde condensate with lesser amounts of the softer linear epoxideresins. Similarly, the amounts of mixed ester used may be adjusted toproduce variations in hardness of the final conversion products.

It is therefore apparent from the above description that widely varyingratios of reactants can be beneficially used in this invention. Forexample, if .an alkali-sensitive coating is desired, a slight excess ofacid could be conveniently used in preparing the mixed ester, or forcertain other applications, it may be desirable to use a larger amountof a complex polyepoxide to increase the chemical resistance. In stillother instances, flexibility may be increased in a given composition byemploying a mixed ester which contains a relatively large amount of along chain organic acid. Alternatively, flexibility, as: well astoughness, may be imparted by larger amounts: of a predominantly linearammonia derivative-aldehyde condensate. In general, while a large excessof the polyepoxide or mixed ester may be desirable for specificapplications, most often equivalent or near equivalent ratios ofpolyepoxides and mixed esters are employed. The 2:1 to 1:2 ratios havebeenfound to give the best over-all characteristics and are thereforepreferred, al though ratios as high as 1:8 and 8:1 may be used.Equivalents as expressed refer to the weight of the poly epoxide perepoxide group, in the instance of the poly epoxides, and the weight ofthe ester per hydroxyl group, in the instance of the mixed esters. Theammonia derivative-aldehyde condensates are employed to makeup from5-85% of the composition by weight, but it is usually suflicient to useabout 10% on a weight basis.

The combination of epoxides, mixed esters, and ammoniaderivative-aldehyde condensates is of utility as a mixture or at varyingintermediate stages of reaction. Thus initial mixtures or intermediatereaction products. which are soluble in common organic solvents may beblended in solution in proper proportions and applied as a coating orimpregnant for fabrics or paper, or for the formation of protectivecoating films. Heat may then be applied to remove the solvent and bringabout polymeri zation to the insoluble, infusible state. In certainother instances, as for molding compositions, the initial mixture orintermediate reaction of the three reactants described may be usedwithout a solvent, giving directly a composite which, on the applicationof heat, converts to a final infusible product.

V For the preparation of a composition such as a semiliquid adhesive,syrupy ammonia derivative-aldehyde condensates which are essentiallyincompletely condensed methylol derivatives, a relatively low meltingpolyepoxide and mixed ester having a softening point below 100 C.(Durrans? Mercury Method) might advantageously be used. For variousother applications, solid or very viscous compositions may be desirable,in which case partially polymerized mixtures would be beneficially used.

In making the new compositions and products herein described, theepoxides, the mixed esters, and the ammonia derivative-aldehydecondensates may be used in regulated proportions without the addition ofother materials. However, for certain end uses additional ingredientsare often advantageously employed including filling and compoundingmaterials, pigments, etc. For the compositions which tend to givesomewhat brittle products on heat conversion to the insoluble, infusiblestate, plasticizers may be added. However, in most instances it ispossible to so regulate the proportions of the three reactingingredients as to obtain products with suitable flexibility, obviatingthe necessity for plasticizers.

The polymerization of mixtures of epoxide, ammonia derivative-aldehydecondensate, and mixed esters may involve several chemical reactions. Itwill be appreciated that the chemical reactions involved are verycomplex and the extent to which each takes place will vary'with thetemperature, the time of heat treatment, and with the nature of thethree reactants employed. While it is not intended to be limited by anytheoretical explanation of the exact nature of these reactions, it seemsprobable that conversion to the final polymeric products, by reactionbetween the three reactants described, involves direct polymerization ofthe epoxide groups inter. se; ammonia derivative-aldehyde condensation;reaction of epoxide groups with active hydrogen-containing groups suchas: methylol hydroxyl. groups, phenolic hydroxyl groups, and amine oramide hydrogens of the ammonia derivative,

all of which take place tosome extent simultaneously in forming thefinal products.

The present invention provides a Wide range of reaction compositions andproducts, including initial mixtures. of the aforesaid epoxides, ammoniaderivative-aldehydecondensates, and mixed esters, their partial orintermediate reaction products. as well as final reaction products. In

general, the initial mixtures as well as the intermediate reactionproducts, unless too highly polymerized, are soluble: in organicsolvents of the type used in lacquers. such as ketone and estersolvents.

In addition to having outstanding physical properties, such as hardness,toughness,v and flexibility, the final in fusible, insoluble productshave outstanding chemical properties, such as high resistance tooxidation, water, alkali, acids, and organic solvents. It has also beenobserved. that the final conversion products possess unusually goodadhesion to. most. surfaces including metal, glass, wood, and plastics.This property of outstanding adhesion: to' a wide variety of-surfacesgives the subject' products high potential value for use in formulatingad hesives. This property is also of extreme value in formulatingprotective coating films for use on many types ofi surfaces. Theadhesion characteristics are probably due to the fact that even in theconverted, infusible state, the compositions contain a high percentageof highly polar groups, such as methylol groups, ether groups, amidegroups, and amine groups. Despite this percentage of polar groups in theinsoluble, infusible products of this.

invention, tolerance for water is unusually low, apparently due to thehigh molecular weight and rigid crosslinked' structure of thecompositions.

Examples 22 through 86', inclusive, illustrate the preparation of'insoluble, infusible protective coating films from the mixtures ofammonia derivative-aldehyde condensates, p'olyepoxi'd'es, and mixedesters. In the preparation of these heat-cured protective coating films,each of the resinous mixed esters was dissolvedin methyl ethyl ketone.The polyepoxides were dissolved in methyl ethyl ketone or xylene to anonvolatile content of 4060%, while the ammonia derivative-aldehydecondensates were dissolved in amixture of methyl ethyl ketone andbutanol. Mixtures of the mixed-ester solutions with the poly epoxidesand ammonia derivative-aldehyde condensates were found to be stable atroom temperature up to at least 168 hours. Mixtures of the solutionswere spread on panels with a .002" Bird applicator and the films werebaked for varying periods of time at 175-200. C. Proportionshereinafterexpressed refer to parts by Weight and: are based on thenonvolatile content of the solution ofreactants.

7 Film resistance Parts of poly- Parts of Parts of Baking Ex. No;epoxide mixed ester aldehyde schedule, 5% aquecondensate min./ G.Boiling ous' water, hr. NaOH at 25C., hr.

1.7 Epon 1001. 5.0 Ex. 7% 168 22.9 Epon 1004;. 5.0 Ex. 7% w 168v 22.2Epon 1007. 2.5 Ex. 7% t 168 9.8 Epon 1001'. 5.0 Ex. 3 128' 22.2 Epon1007. 2.5 EX. l6 5 168 8.1 Epon 864.... 5.0 Ex. 7% 168 12.1 Epon 1001.5.0 EX. 7% 168 18.0 Epon 1004-.- 5.0-Ex. l4: 168. 6.8 ED011864. 5.0 Ex..4 Ex. 168 15.1 Epon 1004. 5.0 Ex. .0 Ex. 7% 120 5.7 Epon 864. 5.0 Ex..1 Ex. 7%. 1 168 8 2 Epon 1001 5.0 Ex. .3 Ex.. 7%,. 168 15 O Eopn 1007.2.5 EX. .8 Ex. ,6 1 168' 19.3 Epon 1004 5.0 Ex. 2.4 Ex. 8" 168 20.0 Epon1007. 2.5 Ex. 2.2 M2 168 1.0 Epon 864.... 4.0 Ex. 5.0 Ext 2% 4 do. 8.0Ex. 1.0 Ex. %2 168 .-...do 1.0 Ex. 8.0 Ex. A 6.4 Ex. 5.0 Ex. 1.1 Ex. 7%16 8.3 Ex. 5.0 Ex. 1.3 Ex. 5 is 6.6 Ex. f5.0 Ex. 1.2 Ex. -7 $6 8.3 Ex.5.0 Ex. 1.3 Ex. 7% is 7.5 EX. -5.0 Ex. 1.3 Ex. 1% /6 8.3 Ex. 5.0'Ex. 1.3Ex. 2% L is 4.9 Ex. 5.0 Ex. 1.0 Ex. /1 1 $6 6.4 Ex. 5.0 Ex. 1.1 Ex. 1M2ls 4.9 Ex. 5.0 Ex. 1:0 Ex. l 54- 4.3 Ex. Ex. 0.9 Ex. 6 is 5.6 Ex. 5L0Ex.1.1 Ex. 7% $6 5.5 Ex. 5.0 Ex. 1.1 Ex. 1% 7.5 Ex. 5.0"Ex. 1.3 Ex. 18 8'M2- 1.2 Ex. 5.0.EX. 0.6 Ex. 19.... 30/200 8' 168- 6.7 EX. 5.0 Ex. ,1.2Ex. 19-.-- /200 M2 4 W oo%mwwfl 4n ooms oo w W wn-O .1 1 1 1 M .0 s e T2 2 m 4 8 m3 8M8 8%2 F mm w M w mmmmmwmmmmmmmm mmmtm mmawmwawwowwwwmmmwasama mwmawm 2 Parts of aldehyde condensatemmmmmmmmmmmnmmmnmnnnn EEEEE Parts of mixed ester 050 .wmmwmmm1121,

Parts of polyepoxide Ex. N0.

1LOEx. 11. 8.0Ex.10 Ex 10 It should be appreciated that while there areabove dis- 3. The composition of matter as described in claim 1 closedbut a limited number of embodiments of this inwherein the pentanoic acidof (A) is 4,4 bis(4-hydroxyvention, it is possible to produce stillother embodiments phenyl)pentanoic acid. without d 4. The composition ofmatter as described in claim 3 wherein the modifying organic acid of (A)is at least one unsaturated aliphatic monocarbo eparting from theinventive concept herein disclosed.

xylic acid having from It is claimed and desired to secure by LettersPatent: 1. A new composition of matter co ble condensation productobtained ester of a polyhydric alcohol havin mprising the insoluabout 10to about 36 carbon atoms.

by heating (A) an 5. The composition of matter as described in claim 3 ga molecular weight 40 wherein (B) is a polyglycidyl ether of a member ofthe of not more than about 8,000 and a mixture of 1) a group consistingof polyhydric phenols and polyhydric 3m 3 m .mm b .mP cm ca e .m .md t Pa md b b m .H I .H S mm w km dm so a a r. I m n w am am. $3 P .m m m .nm m am m m O) O) CBCCB .e e

c mmmnnm r .r w mmla a WP w 5 having functional groups selected from thegroups consistcontaining an average of more than one oxirane group permolecule wherein said is composed of oxirane and hydroxyl ing of (l)oxirane groups and (2) groups.

polyepoxide 0 5 p .nu mm b 6 mm m 0 ma. Wm w d1 m s s m $0 0 m. m e m mmwe t m 2 mo. en 6 eg n mo e group consistconsisting of --OH, -COO,ethereal oxygen and oxirane groups, and

(C) a fusible condensation product organic ammonia derivaof formaldehydeand at least one 9. The composition of matter as described in claim 3tive selected from the wherein (C) is an urea-formaldehyde condensate.mel

group consisting of urea, thioure amine, p-toluenesulfonamide, and alkylderivativ erein (C) is a thiourea-formaldeh 11. The composition ofmatter as wherein (C) is a thiourea-urea form thereof.

yde condensate.

3m mmm t anew .mmi m wewm 10 db 0 mm a cd d 12. The composition ofmatter as des wherein (C) is a melamine-formaldehy alkyl groups of onecarbon i No references cited.

atom.

1. A NEW COMPOSITION OF MATTER COMPRISING THE ISOLUBLE CONDENSATIONPRODUCT OBTAINED BY HEATING (A) AN ESTER OF A POLYHYDRIC ALCOHHOL HAVINGA MOLECULE WEIGHT OF NOT MORE THAN ABOUT 8.000 AND A MIXTURE OF (1) APENTANIOC ACID CONSISTING ESSENTIALLY OF 4,4 BIS(4-HYDROXYARYL)PENTANIOC ACID WHEREIN THE HYDROXYARYL RADICAL IS A HYDROXYPHENYLRADICAL AND IS FREE FROM SUBSTITUENTS OTHER THAN ALKYL GROUPS OF FROM1-5 CARBON ATOMS AND (2) AT LEAST ONE ALIPHATIC MONOCARBOXYLIC ACIDHAVINAG FROM ABOUT 10 TO ABOUT 36 CARBON ATOMS, (B) A POLYEPOXIDECONTAINING AN AVERAGE OF MORE THAN ONE OXIRANE GROUP PER MOLECULEWHEREIN SAID POLYEPOXIDE IS COMPOSED OF THE ELEMENTS CARBON, HYDROGENAND OXYGEN AND HAVING OXYGEN PRESENT ONLY IN THE GROUPS SELECTED FROMTHE GROUP CONSISTING OF -OH, -COO-, ETHEREAL OXYGEN AND OXRIANE GROUPS,AND (C) A FUSOBLE CONDENSATION PRODUCT OF FORMALDEHYDE AND AT LEAST ONEORGANIC AMMONIA DERIVATIVE SELECTED FROM THE FROUP CONSISTING OF UREA,THIOUREA, MELAMINE, P-TOLUENESULFONAMIDE, AND ALKYL DERIVATIVES THEREOF.